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The electron affinity of molecules is a complicated function of their electronic structure. For instance the electron affinity for benzene is negative, as is that of naphthalene, while those of anthracene, phenanthrene and pyrene are positive. In silico experiments show that the electron affinity of hexacyanobenzene surpasses that of fullerene. [5]
Electron affinity can be defined in two equivalent ways. First, as the energy that is released by adding an electron to an isolated gaseous atom. The second (reverse) definition is that electron affinity is the energy required to remove an electron from a singly charged gaseous negative ion.
In that case, the ionization energy decreases as atomic size increases due to adding a valence shell, thereby diminishing the nucleus's attraction to electrons. [12] [13] Ionization energy and electron affinity between two electronegative atoms (i.e., Chlorine and Bromine) decreases as the space between the valence shell and nucleus increases.
By inserting the energetic definitions of the ionization potential and electron affinity into the Mulliken electronegativity, it is possible to show that the Mulliken chemical potential is a finite difference approximation of the electronic energy with respect to the number of electrons., i.e., = = +
A chlorine atom has seven electrons in its third and outer electron shell, the first and second shells being filled with two and eight electrons respectively. The first electron affinity of chlorine (the energy release when chlorine gains an electron to form Cl −) is 349 kJ per mole of chlorine atoms. [1]
A similar theorem (Janak's theorem) exists in density functional theory (DFT) for relating the exact first vertical ionization energy and electron affinity to the HOMO and LUMO energies, although both the derivation and the precise statement differ from that of Koopmans' theorem. [8]
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In chemical physics and physical chemistry, chemical affinity is the electronic property by which dissimilar chemical species are capable of forming chemical compounds. [1] Chemical affinity can also refer to the tendency of an atom or compound to combine by chemical reaction with atoms or compounds of unlike composition.